Normally liquid hydrocarbon compositions containing amidatriazales

ABSTRACT

3-salicylamido and 3-benzosalicylamido-1,2,4-triazoles are provided which are useful in the enhancement of the resistance of olefin polymers to heavy metal-catalyzed oxidative deterioration. Stabilizer compositions consisting essentially of at least one olefin polymer stabilizer and such amidotriazoles; olefin polymer compositions, such as propylene polymer compositions, containing such amidotriazoles and a process for enhancing the resistance of olefin polymers to copper-catalyzed degradation by incorporation of such amidotriazoles or such stabilizer compositions are also provided.

United States Patent Minagawa et al.

1 Sept. 23, I975 2.953.491 9/1960 Hardy et :al. 260/308 R 3.008.941ll/l96l Lynn H 260/308 R 3.647.814 3/1972 Greenfie 260/308 R 3.79l.8032/1974 Andress at al. 44/63 3.813.400 5/l974 Boyle ct al. 260/308 RPrimary Examiner-Danicl E. Wyman Assistant E.\'uminer--Y. H. Smith [57]ABSTRACT 3-salicylamido and 3-benzosalicylamido'l .2,4-triazoles areprovided which are useful in the enhancement of the resistance of olefinpolymers to heavy metalcatalyzed oxidative deterioration.

Stabilizer compositions consisting essentially of at least one olefinpolymer stabilizer and such amidotriazoles; olefin polymer compositions.such as propylene polymer compositions, containing such amidotriazolesand a process for enhancing the resistance of olefin polymers tocopper-catalyzed degradation by incorporation of such amidotriazoles orsuch stabilizer compositions are also provided.

5 Claims, No Drawings t NORMALLY. LIQUID HYDROCARBONCOMPOSITIONSCONTAINING .AMIDATRIAZALES This application is a division ofSer. No. 211,647, filed Dec. 23,1971, now U.S. Pat. No. 3,849,370.

Polypropylene is atough, hard. relatively flexible,hig'h-meltingpol-ymeric material, and thus has a number of importantapplications, such as, for example, as electrical insulation, for copperwires and cables. How.- ever' in several respects thestability ofpolypropylene leaves much to be desired. The polymer shows a tendency todecrease rapidly in melt viscosity and then to become brittle when keptat elevated temperatures for the time required in milling, calendering,extrusion, injection molding, and fiberforming equipment. This deterio rationislparticularly serious when the polymers are worked in a moltenstate in the presence of oxygen, for example, air. It is known in theart that degradation in one or more: physical properties ofpolypropylene due to heat can be inhibited by the incorporation of anumber of well known thermal antioxidants, including hindered phenols,secondary aromatic amines, organic phosphites, and thiodipropionic acidesters. v

A special problem is presented when the polypropylene is contaminated byoris used in contact with a heavy metal suchas copper. Thus,polypropylene employed as insulation for copper wires and cables becomesuseless after a few months. in fact, it has been found that oxidativedegradation of polypropylene occurs at an extremely rapid rate in thepresence of copper, even when the polymer contains effectiveantioxidants. Hansen et al, Journal of Polymer Science, Part A, 2,587-609 (1964), report at page 589 that The catalytic effect of copperon the thermal oxidation of polypropylene is not as drastic in theabsence of antioxidants as it is in their presence. (Emphasis added).Where polypropylene contains antioxidant, in the presence of copper therate of oxidation becomes rigid and constant after a drasticallyshortened induction period compared with .that obtained in the absenceof copper. (page 590). The induction period in oxygen at 140C forpolypropylenestabilized by the addition of 0.5+weight percent of4,4-thiobi's (3-methyl-6-tertbutylphenol) is decreased from about 400hours to 40 hours by the presence 'of copper. Similar 90% losses in theeffectiveness of this antioxidant in the presence of copper have beenobserved over a range oftemperabe unsatisfactory for a variety ofreasons. Most of them did not diminish the catalytic-activity of copperand coppercompoundsl Some actually accelerated the already rapidcopper-catalyzed oxidation of poIypropyL. I ene, andmight'beusefulinotherreactions where oxidation is sought rather than'avoided.The best of the con ventional vdeactivators (for example, N,N-di-B-naphthyl-p-phenylenediamine) were only slightly efj fectiveincurtailingthe catalytic activity of copper." lt

quinolinol, N,N"disalicylidene-l,2-propan.ediamin'e,,

and benzimidazole, either were ineffective or only.

slightly effec'tivefi'an'd usually had other disadvantages,including"instability, incompatibility, wa ter-solubility,volatility.formation-of highly colored products; and reaction withothe'r'components of the'polypropylene composition. i

A number of compounds have been suggested, for use insuppressingcopper-catalyzed oxidation of polypropylene. Hansen et al, supra, andBritish Pat. No. 974,274, to Western Electric Company, Inc, recommendedoxamide and compounds derived from oxamide which contain the radical NHfi-j -NH: I

for inhibiting copper-catalyzed oxidation of polypropylene. Hansen et'alreported that polypropylene com positions containing O.5% byweightantioxidant and 0.5% by weight oxamide or substituted oxamide r etainedbetween 30 to 80% of the effectiveness of the -u'seful ascopperdeactivato'rs and inhibitcoppercatalyzed oxidation ofpolypropylene are known. US.

Pat. No. 3,110,696 to Dexter discloses compounds of wherein the Rradicals are hydrogen, alkyLalkoxy or phenyl. Dexter prefersdihydrazides having the formula where R is an alkyl of up to sixteencarbon atoms,

mono-aryl or naphthenyl, having from five to twelve carbon atoms. Suchcompounds'are shown to reduce the stabilizing effectiveness of dilaurylthiodipropi onate in the presence of copper by about British Pat. No.994,116 to Shell teaches that stabi- 1 liz'er combinations whichc.ontain (a) an organicsulfur compound of the type R S g-R ,-wherein xis an integer.

of up to 2 andR and R; are alkyl, aralkyl, or cycloal kyl, having fromeightto, twenty-five carbon atoms and i Nsalicylidene-Nsalicylhydraz-ide.-. w

US. Pat. No. 3,117,104 to Brown et al discloses oxa (b) a polynuclearpolyphenol consisting of a benzene ring substituted with n3,5-d'ialkyl-4-hydroxybenzyl groups wherein n is 3 or 4, are effectivein protecting alkene polymers, prepared bya low-pressure polymerizationprocess, such as the Ziegler process, against deterioration caused bylight, heat and oxygen. However, it is stated that these stabilizercompositions are incapable of protecting the polymer effectively againstdeterioration in properties caused by contact between copper andpolymer. In discussing the prior art, it is indicated that British Pat.No. 890,761 discloses stabilizer combinations offering protectionagainst deterioration caused by contact between copper and polymer, viz.a combination comprising a diester of a beta-thiodipropionic acid and abis-phenol obtained by the condensation reaction of 1 mol of saturatedaldehyde or ketone having 4 to 6 carbon atoms or of sulphur dichlorideand 2 mols of a phenol having a non-reactive ortho substituent and anon-substituted para ring carbon atom. British Pat. No. 951,931 alsodiscloses the incorporation of a diester of beta-thiodipropionic acid incombination with a certain trisphenolic compound which is obtained bythe condensation reaction of either 1 mol of unsaturated aldehyde orketone and 3 mols of phenol having a non-reactive ortho or parahydrocarbon substituent, or 1 mol of hydroxyaryl-substituted saturatedaldehyde or ketone and 2 mols of phenol having a nonreactive ortho orpara hydrocarbon substituent, into polymers in order to stabilize thelatter against deterioration caused by contact with copper.

However, British Pat. No. 994,116 states at page 2, column 1, thatstability of such polymer compositions containing the relevantstabilizer combinations comprising these diesters plus said bisortrisphenolic compounds leaves much to be desired when these compositionswhether or not in contact with copper are exposed to elevatedtemperatures. This gives rise to serious difficulties during themanufacture of the insulated electric conductors from which theinsulating material consists of such stabilized compositions, sincethese are manufactured by coating the conductor with heat-plastified ormolten polymer material. As is known, high temperatures, generallyhigher than 150C, are used which such coatings are applied. Moreover,electric conductors coated with such stabilized compositions are, ofcourse, not very suitable for use at elevated temperatures.

British Pat. No. 994,116 suggests that this problem can be met byincorporating in the polymer together with the organic sulfur compoundand a polynuclear polyphenol, a bisor trisphenolic compound obtained bythe reaction of either a saturated or unsaturated aldehyde or ketone, ofsulfur dichloride, and a phenol having at least one ortho-ring carbonatom bound to a secondary or tertiary alkyl group. Apparently, the bisortrisphenolic compound when employed with the above stabilizers protectsthe polymer against deterioration caused by contact between copper andpolymer even when the polymer is exposed to elevated temperatures, suchas 150C and above.

British Pat. No. 951,936 to Imperial Chemical Industries, Limited,discusses the problem of protection of polyolefins containing phenolicantioxidants against copper-catalyzed oxidative deterioration. Thephenolic compounds are said to be especially effective as antioxidantswhen they are used in conjunction with an organic sulfur compound havinga molecular weight of at least 250. This patent provides a polymericcomposition suitable for use in close contact with copper, whichcomposition comprises a solid polymer of propylene, particularlyisotactic polypropylene, a phenolic antioxidant, and non-volatileprimary or secondary aromatic or aliphatic amino compounds, thesecondary aromatic amino compounds having at least one nitrogen atom towhich is attached not more than one aryl group. These amines are, ingeneral, not those which are generally peferred as antioxidants inrubber and plastics. Many of these amino compounds, e.g.,p-aminoacetanilide, do not confer any extra protection on polypropylenestabilized with mixtures of phenolic compounds and sulphur compounds inthe absence of copper and do not prevent the degradation ofpolypropylene in the presence of copper when they are used in theabsence of the phenolic stabilizer. The aliphatic amino compoundsusually cause less staining than the aromatic amino compounds, the acidhydrazides being particularly good in this respect.

US. Pat. No. 3,367,907 to Hansen teaches polyolefin compositionsstabilized against degradation accelerated by the presence of copper.There is incorporated in the polymer an antioxidant, such as a phenol,and a copper inhibitor, which can be any azimidobenzene containing theradical:

or any corresponding benzotriazine characterized by the structure Inaccordance with the instant invention, 3- salicylamido and3-benzosalicylamido-1,2,4-triazoles are provided, useful in olefinpolymer compositions, such as polypropylene, containing one or moreolefin polymer stabilizers, which come in contact with heavy metals suchas copper.

In the presence of such amidotriazoles, the usual catalytic effect ofheavy metals such as copper on the rate of degradation of the olefinpolymer is not observed, and instead, the olefin polymer displays aresistance to such degradation, enhanced by the usual olefin polymerstabilizer or stabilizer system, that is virtually as high as though theheavy metal were not present. This is especialy surprising in view ofthe fact that heavy metals substantially reduce the effectiveness ofmost commercially available antioxidants in olefin polymers, even whenso called conventional metal deactivators are incorporated in thepolymer.

Further in accordance with the instant invention, stabilizer systems forolefin polymers are provided consisting essentially of at least oneolefin polymer stabilizer and; 3-salicylamido and3-benzosalicylamido-l,2,4- triaioles of the invention, to substantiallyreduce and in many cases overcome any deleterious effect of heavy metalon the olefin polymer stabilizer or olefin polymer.

In addition, in accordance with the invention, olefin polymercompositions are provided, such as propylene polymer compositions,consisting essentially of olefin polymer and at least one amidotriazoleof the invention.

Olefin polymer compositions of the invention containing theseamidotriazoles can be used on contact with heavy metal such as copperand can be combined with the usual olefin polymer stabilizers to enhancere sistance to oxidative deterioration. Consequently, such olefinpolymer compositions can include, optionally, at least one olefinpolymer stabilizer.

Further, in accordance with the instant invention, a process forenhancing the resistance of olefin polymers, such as propylene polymers,to heavy metal-catalyzed oxidative deterioration is provided, whichcomprises incorporating in the olefin polymer at least one amidotriazoleas defined herein, and optionally, at least one olefin polymerstabilizer.

The olefin polymer stabilizers which can be employed in the inventioninclude, for instance, phenols, organic phosphites, thiodipropionic acidesters, polyvalent metal salts of organic acids, and hydrocarbonsulfides and polysulfides, and conventional olefin polymer lightstabilizers as will be seen hereinafter.

The 3-salicylamido and 3-benz0salicylamido-1,2,4- triazoles inaccordance with the invention have the following structure:

wherein:

a. R is selected from the group consisting of hydrogen and alkyl havingfrom one to four carbon atoms;

b. Z is selected from the group consisting of hydroin which A isalkylene having from one to about eight carbon atoms;

c. X is selected from the group consisting of oxygen and sulfur;

d. Z is a benzene or naphthalene ring substituted by from one to two Rgroups and from zero to two R groups, and i. R is selected from thegroup consisting of OH,

5 SH, SR (where R; is selected from the the group consisting of alkyland alkylene carboxyalkyl having from one to four carbon atoms), and

(where X is as in (0) above) and at least one R is in the orthoposition);

ii. R is selected from the group consisting of alkyl phenyl, alkylphenyl, alkoxy, acyl, acyloxy, phenoxy and alkyl phenoxy having from oneto about eighteen carbon atoms, halogen and amino; and

where Y is selected from the group consisting of oxygen, sulfur,

x N ll 01 where n is one or two and m is zero, one or two.

When Z is a naphthalene ring, the compounds take the form:

where n and m are as in II.

Exemplary R and R R R R and Z alkyl groups include methyl. ethyl,propyl, isopropyl, n-butyl, secbutyl. tert-butyl, pentyl, hexyly heptyl,y o 1..

octyl, nonyl, decyl; undecyl, dodecyl, myristyl. palmityl and stearyl. vI

Exemplary 'Z, alkylaryl groups. include tolyl. methyl, naphthyl, xylyl,mesityL'ethyl phenyl, dodecyl phenyl, nonyl phenyl, and hexyl phenyl.

Exemplary A alkylene groups include ethylene, propylene, hexylene,octylene. butylidene. butylene, ethylidene, propyliden e,isopropylidene, isobutylidene, and pentylene.

Exemplary SR groups are thiomethyl, thioethyl, thiopropyl, andthiobutyl, thioethylene carboxyethyl, thiomethylene carboxymethyl, andthiopropylene carboxymethyl.

Exemplary halogen are fluorine and chlorine.

Exemplary R acyl and acyloxy are acetyl, propionyl, butyryl; acetyloxy,propionyloxy and butyryloxy, myristoyl; myristoyloxy, stearoyl,stearoyloxy, dodecoyl and dpdecoyloxy.

. Exarnplary Z alkylenealkoxy and'alkylenearyloxy includeethyleneoxyethyl, methyleneoxybutyl, ethyleneoxypropyl methyleneoxypalmityl, propylene oxyhexyl, methylene oxyphenyl, ethyleneoxybenzyl, ethylene oxyxylyl, propylene oxymesityl, and ethyleneoxyphenylethyl. I

Exemplary Z heterocyclic include pyridyl, piperidyl, pyrrolyl, andpyrazolyl, pyrimidyl, pyrazinyl and pyridazinyl.

Exemplary Z, aryl include phenyl and naphthyl.

The following Examples illustrate the preparation of the amidot-riazolesof the invention:

5.5 parts of 1,4-bis-(-(3-amino-1,2,4-triazole)) butane and 20.0 partsof phenyl salicylate were reacted at 180C for 4 hrs., and 100 vol. partsof methanol were added and refluxed for l hr. 8.0 parts of white powderwas recovered by filtration. (mp. 316 321C) Elemental Analysis: C% H% N%56.82 4.90 24.36 (Calc.) (57.12 (4.79) (24.23)

' Melting Point Ill-336C. HO

3.6 parts of 3-amino-l,2,4-triazole and 10.4 parts of 5-chlorosalicylicacid phenyl ester were reacted at 170C for 1 hr.. and 100 vol. parts ofmethanol were added and refluxed.7.3 parts of white crystalline powderwere recovered by filtration. (mp. 331336C) ElcmentalAnalysis: c9, H71N71, 1 1 45.10 3.00 23.28 V (011C (45.29) (2.96). (23.48) Cf v MeltingPoint 01-1' wCONHfili-|l 313-320C.

N CH 13.2 parts of 2-hydroxy-3-naphthoic acid phenyl ester and 4.3 partsof 3-amino-1,2,4-triazole were reacted at' 140C. for 3 hrs. Afterheating with 50 parts of methanol, 1.5 parts of colorlesspowd er wasobtained after filtration and drying.

7.8 parts of salicyclic acid chloride was added dropwise into a mixtureof 9.5 parts of S-phenyloxymethyl- 3-amino-1,2,4-triazole and 40 partsby volume of xylene at room temperature, and reacted at 130C. for 3 hrs.after neutralization with sodium bicarbonate and heating with parts byvolume methanol, 12.1 parts of white powder was obtained.

Elemental Analysis: 0% rm N% 61.90 4.59 18.12 .(Calc.) (61.92) (4.55)(18.06) E. Melting Point Ho" 294-302c. O -coNH-|c| 1n N C-CH;

A mixture of 9.7 parts of 3-amino-5-methyl-l,2,4- triazole. 21.4 partsof phenyl salicylate and 50 parts by volume of xylene were refluxed for3 hours. After heating with 100 parts by volume of methanol, 9.9 partsof white powder was obtained.

Elemental Analysis: H% N92 54.99 4.70 26.01 (Calc.) (55.03) (4.62)(25.71)

Melting Point HQ 300C.

coNH c 1 l N C-Cfl-l 4.2 parts of 3-amino-5-ethyl-l,2,4-triaz0le and 11.5 parts of phenyl gentisate were added to 30 parts of ethyleneglycoldimethylether, and reacted at 150C. for 3 hours. Then solvent and phenolwere eliminated, and the residue heated with methanol. After filtrationand drying, 6.7 parts of pale yellow powder was obtained.

Elemental Analysis: C% 1 1% N% 53.27 4.89 22.61 (Cale) (53.22) (4.87)(22.57)

Melting Point 290300C.

Elemental Analysis:

10.7 parts of phenyl salicylate and 4.7 parts of 3- amino-1,2,4-triazolewere reacted at 160C. for 1 hour. 40 parts by volume of xylene wereadded and refluxed for 3 hours. After heating with methanol, 5.5 partsof white powder was obtained.

Elemental Analysis: C% H?! N% 52.82 3.99 27.55 (Cale) (52.94) (3.95)(27.45) H. Melting Point 5.5 parts of 5-ethyl-3-amino-1,2,4-triazole and13.8 parts of para-nitrophenyl 2-mercaptobenzoate were reacted at 150C.for 3 hours. After heating with methanol, 6.3 parts of very slightyellow powder was obtained.

13.3 parts of 5,5-methylene bis-salicylic-acidpara- 30 nitrophenylester, 5.0 parts of 5-methyl-3-amino-l ,2,4-

triazole and 40 vol. parts of dimethylformamide were reacted at 145C.for 4 hours. Solvent was eliminated and heat-treated with methanol. 8.4parts of white powder was gained after filtration and drying.

Elemental Analysis: C% H% N% 56.61 4.61 24.80 (Calc.) (56.24) (4.50)(24.99)

J. The following additional compounds have also been prepared, using oneof the above procedures:

N CCH CH g e-M W3 Melting Point 250C. decomposed C. decomposed 200C.decomposed INS-330C.

330C. decomposed 3 3 5C. decomposed 209C decomposed 230C. decomposeddecomposed 250C. decomposed 230C. decomposed The stabilizer system ofthe inventio r icon-iprises one or more compounds of the inventionincombination with at least one olefin polymer stabilizer, and preferably,two or more such stabilizers. It is well known that in the case ofolefin polymers, combinations of stabiliz ers can be complementary, andcan enhance the resistance of the olefin polymer to oxidativedeterioration. Such enhanced stabilizing effectiveness when present inthe olefin polymer stabilizer combination continues to be evidenced inthe presence of the stabilizer system of the invention.

Stabilizer systems of the invention comprising a compound of theinvention and an olefin polymer stabilizer can be formulated andmarketed as such, ready for use by the converter of the olefin polymerinto useful products.

A variety of olefin polymer stabilizers can be employed of which thefollowing are exemplary.

The organic phosphite can be any organic phosphite having one or moreorganic radicals attached to phosphorus through oxygen. These radicalscan be monovalent radicals in the case of the triphosphites,diphosphites and monophosphites, which can be defined by the formula:

in which R R and R are selected from the group consisting of hydrogen,alkyl, alkenyl, aryl', alkaryl, aralkyl, and cycloalkyl groups havingfrom one to about thirty carbon atoms.

Also included are the organic phosphites having a bivalent organicradical forming a heterocyclic ring with the phosphorus of the type:

in which R, is a bivalent organic radical selected from the groupconsisting of alkylene, arylene, aralkylene, alkarylene andcycloalkylene radicals having from two to about thirty carbon atoms, andR is a monovalent organic radical as defined above in the case of R Rand R Also useful in the compositions of the invention are mixedheterocyclic-open chain phosphites of the type:

More complex phosphites are formed from trivalent organic radicals, ofthe type:

in which R is a trivalent organic radical of any of the types of R to Rinclusive, as defined above A particularly useful class of complexphosphite are the tetraoxadiphosphaspiro undecanes of the formula whereR and R are selected from the group consisting of aryl,- alkyl,aryloxyethyl, alkyloxyethyl, aryloxye thoxyethyl, alkyloxyethoxyethyland alkyloxypolyethoxyethyl. I

An especially preferred class of organic phosphites have a bicyclicaromatic group attached to phosphorus through oxygen, with .no or one ormore phenolic hydroxyl groups on either or both of the aromatic rings.These phosphites are characterized by the formula:

in which Ar is a mono or bicyclic aromatic nucleus and m is an integerof from 0 to about 5. Zis one or a plurality of organic radicals asdefined above for R to R taken singly or together in sufficient numberto satisfy the valences of the two phosphite oxygen atoms. Z can also-behydrogen, and can include additional bycyclic aromatic groups of thetype (HO),,,-Ar.

The term organic phosphite" as used herein is inclusive of theabove-described mono-', diand triphosph- .ites.,Usually, the phosphitewill not have more than about sixty carbon atoms.

Exemplary are monophenyl di -2-ethylhexyl phosphite, diphenylmono-Z-ethylhexyl phosphite, diisooctyl monotolyl phosphite,tri-2-ethylhexyl phosphite, phenyldicylohexyl phosphite, phenyl diethylphosphite, .triphenyl phosphite, tricresylphosphite, tri(dimethylphenyl)phosphite, 'trioctadecyl phosphite, triisooctyl phosphite, tridodecylphosphite, isooctyl diphenyl phosphite, diisooctyl phenyl phosphite,tri(toctylphenyl) phosphite, tri(t-nonylphenyl) phosphite, benzyl methylisopropyl phosphite,.butyl dicresyl phosphite. isooctyl di(octylphenyl)phosphite, di(2- ethylhexyl) (isooctylphenyl) phosphite, tri(2-cyclohexylphenyl) phosphite, tri-a-naphthyl phosphite, tri(phenylphenyl)phosphite, tri(2phenyl ethyl) phosphite, monododecylphosphite,di(p-tert-butyl phenyl) phosphite, decyl phenyl phosphite,tert-butyl-phenyl 2-ethylhexyl phosphite, ethylene phenyl phosphite,ethylene t-butyl phosphite, ethylene isohexyl phosphite, ethyleneisooctyl phosphite, ethylene cyclohexyl phosphite,2-phenoxy-1,3,2-dioxaphosphorinane, 2-butoxy' l ,3,2-dioxyphosphorinane,2-octoxy-5,5-dimethyldioxaphosphorinane, Z-cyclohexyloxy-S,S-diethyldioxaphosphorinane, monophenyl phosphite, 2 -ethylhexylphosphiteyisooctyl phosphite, cresyl phosphite, toctylphenyl phosphite,t-butyl phosphite, diphenyl phosphite, diisooctyl phosphite, dicresylphosphite, dioctylphenyl phosphite. didodecyl phosphite, di-anaphthylphosphite, ethylene phosphite, rbutyl cresyl phosphite,phenyl-mono-2-ethylhexyl phosphite, isooctyl monotolyl phosphite andphenyl cyclohexyl phosphite.

Exemplary penta e ryth rityl phosphites are 3,9-

(5,5)-undecane,-. i 3,9-diphosphaspiro-( 5,5 )-undecane I3,9-di-p-tolyoxy-2,4,8,10 tetraoxa-3,9-diphosphaspiro- (5,5)-undecane;3,9-di(methoxyethyl)2,4,8.10- tetraoxa-3 ,9,diphosphaspiro-( 5,5)-undecane; 3- methoxyethyl--isodecyl-2,4,8, l O-tetraoxa3 ,9-diphosphaspiro(5,5 )-"undecane; 3,9-di(ethokyethyl-)- 2,4,8,1.0-tetraoxa-3,9diphosphaspiro-( ,5 )-u nde'cane 3 ,9-di( butoxyethyl)'-2,4-,8,l O-tetraoxa-3 ,9-diphosphaspiro-(-5,5.)-.undecane;3'-methoxyethyl 9 butoxyethyb 2,4,8,10.tetraoxa-3,9-diphosphaspiro-(5,5)-undecane;* 3 ,9-d i(methoxyethoxyethyl) 2,4,8,1O tetraoxa-.3 ,9diphosphaspiro-(.5,5)-undecane:':di(butoxyethoxyethyl-2,4,8,l0-tetraoxa'3,9-diphosphaspiro-(5,5)-undecane; 3,9- 'di( methoxyethoxyethox'yethyl)-2,-4,8', l O-tetraoxa-3 ,9- diphosphaspiro-( 5.,5 undec'ane; 3:9-di(methoxypolyethoxyethyl )=2,4,8, l O-tetraoxa-3 ,9- diphosphaspiro(5,5) unde'cane (where the polyethoxyethyl group has an averagemolecular weight of 350) 3 ,9-di( methoxypolyethoxyethyl )-2-',4,8lO-tetraoxa- 3,9-diphosphaspiro (5*,5) undecane (where thepolyethoxyethyl group has an average molecular weight of 550) i t rExemplary of the bis ary'l phosphites are': bis(4,4-thio-bis(Z-tertiarybutyl-5 methyl-phenol)) isooctyl phosphite, 1 mono('4,4'-thio-'bis'(Ztertiarybutyl-5-methyl-phenol)) di-phenyl phosphite, tri-(4,4"n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol)) phosphite,(4,4'-benzylidene-bis(2-tertiary-butyl-5- methyl-phenol)) diphenylphosphite, isooctyl 2,2'-bis(- parahydroxyphenyl) propane phosphite,tri-decyl 4,4-

n-butylidene-bis(-2-tertiary* butyl,- 5- methylphenol)phosphite,4,4'-thiobis(2-tertiary butyl- 5-methylphenol) phosphite,2-ethylheXyl-2,2' methylene-bis(4-methyl-6-l(:methylcyclohexyl) phe-,nol phosphite, tri(-2,2-bis-(para-hydroxyphenyl)propane) phosphite,tri(-4,4'-thio-bis(Z-tertiary-butyl-S- methyl-phenol) phosphite,;isooctyl-( 2,6-bis( 2 hydroxy-3,5-dinonylbenzyl)-4-nonyl phenyl))phosphite, tetra-tridecyl 4,4 '-n-butylidene-bis( 2-tertiarybutyl-5-methyl phenyl)diphosphite, tetra-isooctyl4,4'-thiobus(2-tertiary butyl-5 methyl phosphite,2,2'-methylene-bis(4-methyl 6-l-methyl cyclo-hexyl phenyl)polyphosphite, isooctyl -4,4'- isopropylidene-bis-phenyl-polyphosphite,2-ethylhexyl- 2,2-methylene bis(4 methyl-6,1'-mehtyl-cyclohexyl) Thealkyl'substitutjed phenols and-'polynulcearphephenyl triphosphite,tetra-tridecyl-4,4'-oxydiphenyl di diphosphite, tetraitetra-n-dodecyl-4,4-n-butylidenebis (2 .nols,*=becauseoffhe-irfniolecularweight; have a higher boiling "point: andtl'i'erfo're are preferred because of their lower volatility. There canbe one or a-plurality of alkyl groups of one or more carbon atoms. Thealkyl group or groups including any alkylene groups between phenolnuclei preferably aggregate at least four carbon atoms. The longer thealkyl or alkylene chain, the better the compatibility withpolypropylene, insasmu ch as the phenolic compound then acquires more ofan aliphatic hydrocarbon character, and therefore there is no upperlimit on the number of alkyl carbon atoms. Usually, from the standpointof availability, the compound will not have more than about eighteencarbon atoms in an alkyl, alicyclidene and alkylene group, and a total.of,not over about fiftycarbon' atoms.'The compounds .mayihave fromoneto four alkyl-radicals per Phenol IlUClGLlSif-s Tzhe phenol containsatleast one "and preferably at least two phenolic hydro'xyls, the two'or"more hydroxyls being in the same ring, if there is only one. In the caseof bicyclic phenols, the rings can be linked by thio or oxyether groups,or by alkylene, alicyclidene or arylidene groups. a; a

,The monocyclic phenolswhich can, .be employed have the structure;

( E-l, O

A whereR is aryl', alkyl or cycloalkyl.

-"of x and x does not exceed six.

The polycyclic phenol employed in the stabilizer combination is onehaving at [least two aromatic nuclei linked by a polyvalent linkingradical, as defined by the formula:

i A ir),, Y-(Ar),.

wherein Y is apolyvalent linking group selected from the groupconsisting of oxygen; carbonyl; sulfur; sulfinyl; aromatic, aliphaticand cycloaliphatic hydrocarbon groups; and oxyhydrocarbon,thiohydrocarbon and heterocyclicgro ups: The linking group can have fromone up to;twenty carbon atoms. Ar is a phenolic nucleus which can be aphenyl or a polycarbocylic group having condensed or separate phenylrings: each Ar group contains at least one free phenolic hydroxyl groupup to a total of five. The Ar rings can also include additional ringsconnected by additional linking nuclei' of the type Y, for example, ArY-Ar -Y-Ar.

m and m are nurr'ib ers from one to five, and n, and n are numbers ofo'neor greater, and preferably from one tofour}.

ems. Examples of such inert substituents include hydrogen, halogenatoms, e.g. chlorine, bromide and fluorine; organic radicals containingfrom one to about thirty carbon atoms, such as alkyl, aryl, alkaryl,aralkyl, cycloalkenyl. cycloalkyl, alkoxy, aryloxy and acyloxy where Ris aryl, alkyl or cycloalkyl, or thiohydrocarbon groups having from oneto about thirty carbon atoms, and carboxyl groups. Usually, however,each aromatic nucleus will not have more than about eighteen carbonatoms in any hydrocarbon substituent group. The Ar group can have fromone to foursubstituent groups per nucleus.

' Typical aromatic nuclei include phenyl, naphthyl. phenanthryl,triphenylenyl, anthracenyl, pyrenyl, chrysenyl, and fluorenyl groups.

when Ar'is a benzene nucleus, the polyhydric polycyclic phenol hasthestructure:

wherein R R and R are inert substituent groups as described in theprevious paragraph, m and m are integers from one to a maximum of five,m is an integer from one to a maximum of four, x, and x are are integersfrom zero to four, and x is an integer from zero to three; y is aninteger from zero to about six and y is an integer from one to five,preferably one or two.

Preferably, the hydroxyl groups are located ortho and/or para to Y.

Exemplary Y groups are alkylene, alkylidene, and alkenylene arylene,alkyl arylene, aryalkylene, cycloalkalene, cycloalkylidene, and oxaandthiasubstituted such groups; carbonyl groups, tetrahydrofuranes, estersand triazino groups. The Y groups are usually bi, tri, or tetravalent,connecting two, three to four Ar groups. However, higher valence Ygroups, connecting more than four Ar groups, can also be used. Accordingto their constitution, the Y groups can be assigned to subgenera asfollows:

I) Y groups where at least one carbon in a chain or cyclic arrangementconnect the aromatic groups, such as q fide, bis(2-tertbutyl-4-hy'droxy-5-inethylphenyl sulfoxide), bis-(3-ethyl-5-tert-butyl4-hydroxyi b'e'nzyl) 'sulfide,bis(2-hydroxy-4-methyl-o-tert-butyl'phenyl) sulfide,4,4"-'bis(4-hydroxyphe nyl)"pentanoic acid octadecyl thiopropionateester, l.l.3-tris(2'-methyl-4'- hydroxy-S -tert-butylphenyl butane, l ,1,3-t-ris-( 1 methyl-3-hydroxy-4-tert-butylphenyl) butane, 1,8-

1 jbis(2Ehydroxy-5-methylbenzoyl-n-octane, 2,2-

ethylene-b is-[4'-(3-tert-butyl-4-hyroxyphenyl)- thiazole], l-methyl-3-(3-methyl-5-tert-butyl-4- hydroxybenzyl)-naphthalene,2,2-(2-butene)bis-(4- 'methoxy--tert-butyl phenol) and pentaerythritolhydroxyphenyl propionate.

A particularly desirable class of polyhydric polycyclic phenols are thedicyclopentadiene polyphenols, which are of the type:

H OH

in which R and R are lower alkyl, and can be the same or different, andn is the number of the groups enclosed by the brackets, and is usuallyfrom 1 to about 5. These are described in US. Pat. No. 3,567,683, datedMar. 2, 1971 to Spacht. A commercially available member of this class isWingstay L, exemplified by dicyclopentadionetri(2-tert-butyl-4-methyl-phenol) of the formula:

The polyhydric polycyclic phenols used in the invention can also becondensation products of phenol or alkylphenols with hydrocarbons havinga bicyclic ring structure and a double bond or two or more double bonds,such as a-pinene, B-pinene, dipentene, limonene, vinylcyclohexene,dicyclopentadiene, allo- Qcimene, isoprene and butadiene. Thesecondensation products are usually obtained under acidic conditions inthe form of more or less complex mixtures of monomeric and polymericcompounds. However, it is usually not necessary to isolate theindividual constituents. The entire reaction product, merely freed fromthe acidic condensation catalyst and unchanged starting material, can beused with excellent results. While the exact structure of these phenoliccondensation products is uncertain, the Y groups linking the phenolicnuclei all fall into the preferred subgenus 1. For method-ofpreparation, see, e.g., us. Pat. No. 3,124,555, us. Pat; No. 3,242,135,British Pat. No. 961,504.

The thiodipropionic acid ester has the following formula: I q

R,OOCCH CH SCl-l CH COOY l in which R is an organicradical selected fromthe group consisting of hydrocarbon radicals suchas alkyl, alkenyl,aryl, cycloalkyl, mixed alkyl aryl, and mixed alkyl cycloalkylradicals;and esters thereof with aliphatic carboxylic acids; and Y is selectedfrom the group consisting of a) hydrogen, b) a second R radical R whichcan be the same as or different from the R radical, c) a polymeric chainof n thiodipropionic acid ester units:

R,O[OCCH CH SCH CH COOXO],,OCCH CH -S- CH CH COOZ wherein Z is hydrogen,R or M; n is the number of thiodipropionic acid ester units in thechain; and X is a bivalent hydrocarbon group of the type of R the valueof n can range upwards from 1, but there is no upper limit on n exceptas is governed by the ratio of carbon atoms to sulfur atoms as statedbelow; and d) a polyvalent metal M of Group ll of the Periodic Tablesuch as zinc, calcium, cadmium, barium, magnesium and strontium. Themolecular weights of the R and Y radicals are taken such that with theremainder of the molecule, the

thiodipropionic ester has a total of from about ten to about sixtycarbon atoms per sulfur atom.

Accordingly, the various thiodipropionic acid ester species comingwithin the above-mentioned categories within the general formula can bedefined as follows:

b. R OOCCH CH SCH CH COOR d. [R,OOCCl-l CH SCl-l CH COO] M In the aboveformulae, R and R M, X and Z are the same as before. In the polymer c),as in the other forms of thiodipropionic acid esters, the total numberof carbon atoms per sulfur atom is within the range from about ten toabout sixty.

The R radical of these esters is important in furnishing compatibilitywith the polypropylene. The Y radical is desirably a different radical,R or M or a polymer, where R is rather low in molecular weight, so as tocompensate for this in obtaining the optimum compatibilityandnonvolatility. Where Y is a metal, the thiodipropionic acid esterfurnishes the beneficial properties of the polyvalent metal salt whichis described below.

The aryl, alkyl, alkenyl and'cycloalkyl groups may, if desired,'containinert, nonreactive substituents such as halogen and other'cai bocyclicand heterocyclic ring structures condensed therewith.

Typical R radicals: are, for example, methyl, ethyl, propyl, isopropylbuty1, isobutyl, t-butyl, amyl, isoamyL n-octyl,isooctyl, 2 -ethylhexyl, t-octyl decyl, dodecyl, octadecyl, allyl, hexenyl, linoleyl,ricinoleyl, oleyl, ,phlenyl xylyhtolyl, ethylphenyl, naphthyl,cyclohexyl be nzyl, cyclopentyl methylcyclohexyl, ethylcyclohexyl, andnaphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl,pentaerythrityl, and polyoxyalkylene radicals suchas those .derived fromdiethylene glycol, triethylene, glycol, polyoxypropylene glycol,polyoxyethylene glycol, and polyoxypropyleneoxyethylene glycol, andesters thereof with any of the organic acids named below in thediscussion of the polyvalent metal salts, including in addition thoseorganic acids 'propionate,

arylene radicals such as phenylene methylenephenylene dimethylenephenylene,

and alicycl'ene radicals such as cyclohexylene and cyclopentyl tAs-exemplary of the thiodipropionic acid esters which can be used, therecan be mentioned the following: monolauryl thiodipropionic acid,dilauryl thiodibutyl stearyl thiodipropionate, 'di(2-ethylhexyl)-thiodipropionate, diisodecylthiodipropionate, isodecylphenyl thiodipropionate, -benzyl lauryl thiodipropionate, benzyl phenylthiodipropionate, the diester of mixed coconut fatty alcohols andthiodipropionic acid, the diester of mixed tallow fatty alcohols andthiodipropionic acid, the acid ester of mixed cottonseedoil fattyalcohols and thiodipropionic acid, the acid ester of mixed soybean oilfatty alcohols and thiodipropionic acid, cyclohexyl nonylthiodipropionate, monooleyl thiodipropionic acid, hydroxyethyl laurylthiodipropionate, monoglyceryl thiodipropionic acid,

glyceryl monostearate monothiodipropionate, sorbityl isodecylthiodipropionate, the polyester of diethylene glycol and thiodipropionicacid, the polyester of triethylene glycol and thiodipropionic acid, thepolyester of hexamethylene glycol and thiodipropionic acid, thepolyester of pentaerythritol and thiodipropionic acid, the polyester ofoctamethylene glycol andthiodipropionic acid, the polyester ofp-dibenzyl alcoholandthidipropionic acid, ethylbenzyl laurylthiodipropionate, strontium ,stearyl thiodipropionate, magnesium oleylthiodipropionate, calcium dodecylbenzyl thiodipropi onate, andmono(dodecylbenzyl) thiodipropionic acid. I These esters are for themost part known compounds, but'wherethey are not available, they arereadily prepared by esterification of thiodipropionic acid and thecorresponding alcohol. l

When the compound is used in conjunction with a polyvalent metal salt ofan organic'acid, the organic acid will ordinarily have from about six toabout twenty-four carbon atoms. The polyvalent metal can be any metal ofGroup II of the Periodic Table, such as zinc, calcium, cadmium, barium,magnesium andstron- I tium. The alkali metal salts and heavyrrietalsalts such as lead salts are unsatisfactory. The acid can be anyorsubstituted, if desired, withnonreactive groups, such as halogen,sulfur and hydroxyl. By the term alicyclic" it will be understood thatthere is intended any cyclic acid in which the ring is nonaromatic andcomposed solely of carbon atoms, and such acids may if desired haveinert, nonreactive substituents such as halogen, hydroxy], alkylradicals, alkenyl radicals and other carbocyclic ring structuresvcondensed therewith; .The oxygencontaining heterocyclic compounds can bearomatic or.

nonaromatic and can include oxygen and carbon in the ring structure,such as alkyl-substituted 'furoic acid. The aromatic. acids likewise canhave nonreactive ring substituents such as halogen,,alkyl and alkenylgroups, and other saturated or aromatic rings condensed therewith.

As exemplary of the acids which can be used in the form of their metalsaltsthere can be mentioned the following: hexoic acid, 2-et hylhexoicacid, n-octoic acid, isooctoic acid, capric acid, undecylic acid, lauricacid, myristic acid, palmitic acid, margaric acid, stearic acid, oleicacid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capricacid, benzoic acid, phenylacetic acid, butyl benzoic acid, ethyl benzoicacid, propyl benzoic acid, hexyl benzoic acid, salicyclic acid,naphthoic acid ,:1-naphthalene acetic acid, orthobenzoyl benzoic acid,naph thenic acids derived from petroleum, abietic acid, dihydroabieticacid, hexahydrobenzoic acid, andmethyl furoic acid. I

The water-insoluble salts are preferred, because tney are not leachedout when the plastic is in contact with water. Where these salts are notknown, they are made by the 'usual types of reaction, such as by mixingthe acid, or anhydride with the corresponding oxide or hydroxide of themetal in a liquid solve'nfland heating, if necessary, until saltformation is complete. l

The hydrocarbon sulf des and polys ulfid es can contain one sulfur atomor two'or more sulfur atoms linked in a'polysulfide"unit. Usually, thesulfides and'polysu lfides will not have more than fifty carbon atoms.They can be defined by the formula;

wherein n is the number of sulfur atoms and ranges from-one to aboutsix,and R is an organic radical having from one to about thirty carbonatoms, such as alkyl, aryl, alkaryl,'aralkyl, and cycl'oalkyl. Thefollowing compounds'aretypical: dibutyl sulfide, didec'yl sulfide,diphenyl sulfide, dibenzyl sulfide, butyl octyl sulfide, di-n-dodecyltrisulfide,-di-tertiary dodecyl disulfide, dipara-tertiary butylphenyl'trisulfide', dibenzyl disulfide, dibenzyl tetra sulfide, anddibenzyl trisulfide.

r Light stabilizers forolefin polymers can also be added, for" example,2'-hydro xybenaophenones, ohydroxyphenylbenzotriazoles, 4 l-dioxides ofa,B-benzoisothiazolone and l,3";5 -triazines and nickel organo- I incontact with heavy metals. such as copper. and can be combined with theusual olcfinpolymer stabilizers by the converter in the usual way.without any modification whatsoever, so as to obtain the benefits of theinvention due to the presence in the formulation of a acid ester. Anadditional fourth ingredient which is inl eluded in the preferredsystems of the invention but which is notessential is an organicphosphite, and a fifth optional ingredient is a polyvalent metal salt ofan organic acid. The olefin polymer stabilizers together give anenhanced stabilization which is not obtainable from any of them alone orin combinations of two with the compound of the invention.

A further improvement'in resistance to degradation is obtained if to thestabilizer composition of the invention there be added polyols, such aspentaerythritol and/or dipentaerythritol; or trimethylol propane;oxyacids such as malic acid, tartaric acid or citric acid; epoxycompounds, such as butylepoxy stearate or borate esters, such as phenyllauryl borate, tristearyl borate and 2,6-di-t-butyl-4-methyl-phenylborate. Only a small amount is sufficient to give a noticeableimprovement. From 0.5 to l% is satisfactory.

The compounds of the invention are not olefin polymer stabilizers.However, where thecompounds of the invention are employed in conjunctonwith an olefin polymer stabilizer, such as a phenol, and athiodipropionic acid ester, and the olefin polymer is in contact withcopper, the polymers resistance to embrittlement and reduction in meltviscosity at elevated temperatures can be almost as high as though thecopper were notpresent. An organic phosphite and/or a polyvalent metalsalt, employed in conjunction with the phenol and thiodipro'pionie acidester and compounds of the invention, can further enhance resistance ofthe polymer to discoloration in the presence of copper. In many cases,an enhanced synergistic stabilizer activity is ob served in suehcombinations.

The compound of the invention can minimize any catalytic effect of heavymetals such as copper, lead, cobalt, and chromium, on the rate ofdegradation of the olefin polymer in the presence of olefin polymerstabilizers. Very small amounts can significantly reduce this effect.Amounts withinthe range from about 0.00l to about 5% by weight of thepolypropylene are satisfactory. Preferably, from 0.05 to l% is employed.

The amount of total stabilizer including the olefin polymer stabilizerand the compound of the invention is within the rangefrom about 0.000lto about 75%, preferably from 0.01 to 5%. Of this. the olefin polymerstabilizer comprises from about 0.001 to about 5% by weight, and thecompound of the invention from about 0.000] to about 5% by weight. Thepreferred olefin polymer stabilizer comprises from about 0.025 to about1% ofa phenol, from about 0.05 to about 1% of a thio- I dipropionic acidester, andoptionall-y, from about 0.05 to about 1.25% of a phosphite,and from about 0.025

to about 0.75% of a polyvalent metal salt, when present.

The compounds of the invention and the olefin polymer stabilizers may beformulated as a simple mixture for incorporation in the polymer by thepolymer manufacturer or by the converter. An inert organic solvent canbe used to facilitate handling, if the ingredients do not form ahomogeneous mixture or solution.

Polypropylene solid polymer can be defined in a manner to differentiateit from other polyolefins as having a density within the range of from0.86 to 0.91, and a melting point above C. The stabilizer of theinvention is applicable to all such polypropylenes, as distinguishedfrom polypropylenes in the liquid form or in semiliquid or gel-likeforms, such as are used as greases and waxes.

The stabilizer system of the invention is applicable to polypropylenesprepared by any of the various procedures, for the molecular weight andtacticity are not factors affecting this stabilizer. lsotacticpolypropylene, available commercially under the trade names Profax,Escon and Olefane and having .a softening of hotworking temperature ofabout 350F., is an example of a sterically regular polypropylenepolymer.

Mixtures of polypropylene with other compatible polymers and copolymersof propylene with copolymerizable monomers also can be improved inaccordance with this invention. For example mixtures of polyethylene andpolypropylene, and copolymers of propylene and ethylene which contain asufficient amount of propylene to present the instability problem thatis resolved by the compounds of the invention, may be improved by theaddition of one or more of .the compounds of the invention, alone or invcombination with other polypropylene stabilizers. 1

The stabilizer systems of the invention may also be used withpolyolefins higher than polypropylene, such as polybutylene andpolyisobutylene.

The compounds of the invention and stabilizer systems including the sameare incorporated in the polymer in suitable mixing equipment, such as amill or a Banbury mixer. If the polypropylene has a melt viscosity whichis too high for the desired use, the polypropylene can be worked untilits melt viscosity has been reduced to the r ed range before addition ofthe stabilizer. However, polypropylenes in a range of workable meltviscosities are now available. Mixing is continued until the mixture issubstantially uniform. The resulting composition is then removed fromthe mixing equipment and brought to the size and shape desired formarketing or use.

The stabilized polypropylene can be worked into the desired shape, suchas by milling, calendering, extrusion or injection molding orfiber-forming. In such operations, it will be found to have aconsiderably improved resistance to reduction in melt viscosity duringthe heating, as well as a better resistance to discoloration andembrittlement on ageing and heating.

The following Examples represent preferred embodiments of the stabilizercompositions and olefin polymer compositions of the invention.

' EXAMPLES 1 TO 3] Polypropylene compositions were prepared, stabilizedby combinations of compounds of the invention and known polyjpropylenestabilizers, and were evaluated for their resistance to oxidativedegradation in the employed, to determine the effective useful life ofthe polypropylene.

The base olefin polymer composition tested was as milled for l minuteson a mixing roll, and the resulting composition was extruded at 250C.through a 30 mm extruder at 30 rpm. Sheets of 0.5 mm thickness wasobtained by compression-molding at 180C. under a presfollows: sure of200 kg/cm for 5 minutes.

P b w I A sandwich was prepared composed of rolled copper ysheet-polypropylene sheet-rolled copper sheet. The Polypropylene 100polypropylene used was 40 X 50 mm and the roller cop- (Profax 659l I persheet used was 0.03 mm thick. The sandwich was l,l,3-tns(2 -methyl-40.07 hydrOXy-S'-tert-butylphenyl) pressed flat with a 145 g. force, andthe degradation of g i f 0 30 the copper sheet evaluated by heating thesandwich at Tr inZn 1 hQn |"i?ii 152C. in a hot pack oven at atmosphericpressure in 3 A nido-l.2,4-tri uzole of 0.30 air. a f igf as [med m Asthe Control, the base composition was tested,

15 without the amidotriazole.

Table I below sets out the results of the test for each The componentsforming the above formulation were COmPOImd st TABLE I Oven Test at152C. Example Hrs. to

No. Compound Failure Color Control None None I CONHC N 584 None H H l NCH 2 Cl- ()NH C N 540 None N ll N CH 3 CONH- 502 None i if n N CH l N H1 4 O coNH fi r]: 610 None N CH HO \N/ P s --coNH r-|1 480 None I N 3H0C..H N H 6 CONHfi-li-|l 600 None N CH f C 2 N Color None None

None

None

None

None

None

None

None

None

Oven Test at I52C. Hrs. to Failure TABLE I -Continued Compound C--C HOC,H

N /CCH Example G-CON HO l6 in -CON HCN TABLE I -Continued Oven Test at152C. Example Hrs. to

No. Compound Failure Color Ho OH 27 lfifi-NHCO- coNH c- N v 481 None mo-c N CC1H1 N NHCSNH H H 28 T$fi-NHCO 301 None HC N \ SC H COOCH 29CONH-C lfi 590 None N C- CH,

Ho 30 @CONHC 407 None CCH20( N H HS 31 @\CONHC- N 521 None N C H, Y

H 32 CONHC N 444 None CCH N H 45 EXAMPLE 32 cut X mm and heated in acirculating airoven at In order to see the effects of theamindotriazoles on until failureimproving the resistance to degradationof polypropylene in the presence of copper powder, sample sheets wereprepared of the following formulation: TABLE II Parts by Weight ExampleI qga j a z V No. Compound to Failure Polypropylene I00 (Profax 6501)Control None I2 I, l ,3-tris( 2'-methyl-4 0.07 3 25-ethyl-3-salicyloylamidohydroxy-S -tert-butylphenyl) l,2,4-triazole 234butane (Topanol CA) 0 Distearyl thiodipropionate 0.30 H Trinonylphenylphosphite 0.13 2-Amido,l,2,4,-triazole 0.30 fi' Copper Powder v 1.50 N CCZH5 2. The formulation was blended on a mill at 185C. 6

for 5 minutes. Then polypropylene sheets 0.4 thick were made bycompression-molding at C. undera The stabilizing effect of theamidotriazole is apparent pressure of 200 kg/cm for 5 minutes. Thesheets -were m e data- EXAMPLE, 33

In order to see the effect of the amidotriazole against heavy metal inpolymerization catalysts, sample polypropylene films were prepared ofthe following formulation:

Parts by Weight Polypropylene I 10 (Profax 650i) Distearylthiodipropiona 0.25 Amidotriazole 0.10

The time required for the film to absorb cc. of oxygen per gram ofsample when heated at 160C. was determined, and is listed in thefollowing Table III:

The stabilizing effect of the amidotriazole is evident from the abovedata.

EXAMPLES 34 TO 37 In order to see the effect of the amidotriazole inenhancing the resistance to degradation of polypropylene in the presenceof heavy metal pigments, sample films were prepared of the followingformulation:

Parts by Weight Polypropylene 100 (Profax 850]) l,l,3-tris(2-methyl-4'-0.07 hydroxy-S '-tert-butylphenyl) butane (Topanol CA) Distearylthiodipropionate 0.30 Trinonylphenylphosphite 0.17 Cu phthalocyanineblue 0.50 Amidotriazole 0.30

2. The hours to failure were measured at 160C. Test results are listedin Table IV:

TABLE IV Example No.

Oven Test at l80C. Hrs.

Compound to Failure Control None 2 l0 TABLE Ill Oven Test at 160C. Hrs.

Example No. to Failure Compound Control 3 3 None3(5-methylsalicyloyl)amidol ,2,4-triazole 30 min.

200 hrs.

The effectiveness of the amidotriazole under these conditions is quiteremarkable.

The amidotriazoles of the invention are also effective antioxidants inany hydrocarbons having a long or short carbon chain. Thus, hydrocarbonfuels, such as gasoline, kerosene, jet fuel, and fuel oil, have anincreased resistance to oxidative deterioration when a compound of theinvention is incorporated therein.

1. HYDROCARBON COMPOSITIONS WHICH HAVE AN ENHANCED RESISTANCE TOOXIDATIVE DETERIORIATION IN PHYSICAL PROPERTIES CONSISTING ESSENTIALLYOF A HYDROCARBON AND AT LEAST ONE 3AMIDO-1,2 4-TRIAZOLE IN HAVING THEFORMULA:
 2. A hydrocarbon composition in accordance with claim 1,wherein the hydrocarbon is kerosene.
 3. A hydrocarbon composition inaccordance with claim 1, wherein the hydrocarbon is a normally liquidhydrocarbon fuel.
 4. A hydrocarbon composition in accordance with claim1, including, in addition, at least one antioxidant selected from thegroup consisting of alkylsubstituted phenols and polynuclear phenols. 5.A hydrocarbon composition in accordance with claim 4, wherein theantioxidant is a alkyl-substituted phenol.